CN106795633B - Etching liquid composition, method for etching multilayer film, and method for manufacturing display device - Google Patents
Etching liquid composition, method for etching multilayer film, and method for manufacturing display device Download PDFInfo
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- C23F1/30—Acidic compositions for etching other metallic material
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Abstract
本发明涉及一种蚀刻液组合物、多层膜的蚀刻方法、和显示装置的制造方法，其中，本发明的蚀刻液组合物包含：(A)铜离子供给源；(B)分子内具有1个以上的羧基的有机酸离子供给源；(C)氟离子供给源；(D)作为第一添加剂的蚀刻调节剂、表面氧化力提高剂、或者这些的组合；以及(E)作为第二添加剂的表面活性剂。
The present invention relates to an etchant composition, an etching method for a multilayer film, and a method for manufacturing a display device, wherein the etchant composition of the present invention comprises: (A) a copper ion supply source; (B) a molecule having 1 An organic acid ion supply source of more than one carboxyl group; (C) a fluoride ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as the first additive; and (E) as the second additive of surfactants.
Description
Technical Field
The invention relates to an etching solution composition, a method for etching a multilayer film, and a method for manufacturing a display device. For example, the present invention relates to an etching liquid composition which can be used for etching a multilayer film containing copper and titanium, an etching method of a multilayer film containing copper and titanium using the etching liquid composition, and a manufacturing method of a display device using the etching liquid composition.
Background
Conventionally, aluminum or an aluminum alloy has been generally used as a wiring material for display devices such as flat panel displays. However, in recent large-sized and high-resolution displays, there is a problem that signal delay due to characteristics such as wiring resistance occurs in aluminum-based wiring materials, and it is difficult to achieve uniform screen display.
Therefore, studies have been conducted on a wiring mainly composed of copper, which is a material having a lower resistance. However, when copper is used for the gate wiring, adhesion between a substrate such as glass and copper is insufficient, and when copper is used for the source/drain wiring, there is a problem that the copper diffuses into a silicon semiconductor film which is a base of the substrate. Therefore, in order to prevent such a problem, a lamination of a barrier film in which a metal having high adhesion to a substrate such as glass and barrier properties that hardly diffuses into a silicon semiconductor film is disposed has been studied. As the metal, metals such as titanium (Ti) and molybdenum (Mo) are being studied, and copper and a multilayer thin film of these metals are being studied.
On the other hand, such a multilayer thin film wiring is formed on a substrate such as glass by a film formation process such as a sputtering method, and then etched using a resist or the like as a mask to form an electrode pattern. As etching methods, there are a wet method (wet) using an etching liquid and a dry method (dry) using an etching gas such as plasma, and among them, the etching liquid used in the wet method (wet) is required to have (i) high processing accuracy, (ii) no generation of etching residue, (iii) high stability and safety of components and easy handling, and (iv) stable etching performance.
On the other hand, as an etching solution generally used in the copper etching process, an etching solution containing hydrogen peroxide as a main component, an etching solution containing persulfate as a main component, and the like are known. However, the etching liquid containing hydrogen peroxide or persulfate as described above has problems of a decrease in productivity and an increase in the amount of waste liquid due to a change with time caused by instability of the liquid, and a risk increase due to heat or gas generated by rapid decomposition.
On the other hand, as an etching solution used in the copper etching process which does not contain peroxide or the like, an ammonia alkaline etching solution containing copper ions and ammonia is known. However, since such an alkaline etching solution has a high pH, a large amount of ammonia may volatilize from the etching solution, and the etching rate may fluctuate due to a decrease in the ammonia concentration, thereby significantly deteriorating the working environment. On the other hand, although evaporation of ammonia from the etching solution can be suppressed by adjusting the pH to a neutral region, in this case, there is a problem that residues are precipitated when rinsing with water. On the other hand, in the case of an ammonia alkaline etching solution containing copper ions and ammonia, titanium etching is difficult to perform.
Disclosure of Invention
Technical problem to be solved by the invention
The present invention provides a novel etchant composition which does not cause the above-described problems and has various advantages described below, a method for etching a multilayer film using the etchant composition, and a method for manufacturing a display device using the etchant composition.
On the other hand, the technical problem of the present invention is not limited to the above. Technical problems of the present invention will be understood by the overall contents of the present specification, and other technical problems of the present invention will be readily understood by those skilled in the art.
Means for solving the problems
In one aspect, the present invention provides an etching solution composition comprising: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive.
Wherein the contents of (a) to (E) in the etching solution composition may be: (A) 0.02-1.0 mol/kg of copper ion supply source; (B) 0.01 to 3.0 mol/kg of an organic acid ion source having 1 or more carboxyl groups in a molecule; (C) 0.01 to 1.0 mol/kg of a fluorine ion source; (D) 0.01-3.0 mol/kg of first additive; (E) the second additive is 1.0-30,000 ppm.
On the other hand, the copper ion supply source (a) may be at least one selected from the group consisting of copper, copper sulfate, copper nitrate, copper chloride, copper fluoride, copper phosphide, copper hydroxide, copper acetate, copper citrate, copper lactate, copper oleate, copper silicide, copper bromide, and copper carbonate.
On the other hand, the organic acid ion source having 1 or more carboxyl groups in the molecule (B) may be at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, gluconic acid, citric acid, tartaric acid, malic acid, succinic acid, oxalic acid, maleic acid, and ammonium salts thereof.
On the other hand, the mixing ratio of the organic acid ion supply source (B) to the copper ion supply source (A) may be 0.01 to 150.0 times on a molar basis.
On the other hand, the fluoride ion supply source (C) may be at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, ammonium fluoroborate, potassium bifluoride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, calcium fluoride, and copper fluoride.
On the other hand, the mixing ratio of the fluorine ion supply source (C) to the copper ion supply source (a) may be 0.01 to 50.0 times on a molar basis.
On the other hand, the etching regulator (D) as the first additive is preferably a source for supplying halogen ions other than fluorine ions. More specifically, the etching regulator may be at least one selected from the group consisting of hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, bromic acid, potassium bromide, sodium bromide, ammonium bromide, iodic acid, potassium iodide, sodium iodide, and ammonium iodide.
On the other hand, the surface oxidizing power improver (D) as the first additive is preferably an inorganic acid. More specifically, the surface oxidizing ability improver may be at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid.
On the other hand, the mixing ratio of the first additive (D) to the copper ion source (a) may be 0.01 to 150.0 times on a molar basis.
On the other hand, the surfactant (E) as the second additive is preferably a nonionic surfactant. More specifically, the surfactant may be at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polyether polyol, polyethylene glycol oleate, gelatin, and Ethylene Oxide (EO) -Propylene Oxide (PO) copolymer.
On the other hand, the etching solution composition may further include (F) an alkali metal salt as a third additive.
The alkali metal salt of the third additive (F) may be at least one selected from halogen-containing alkali metal salts, organic acid alkali metal salts having 1 or more carboxyl groups in the molecule, and strongly basic alkali metal salts.
On the other hand, the content of the third additive (F) in the etching solution composition may be 0.01 to 2.0 mol/kg.
On the other hand, the mixing ratio of the third additive (F) to the copper ion source (a) may be 0.01 to 100 times on a molar basis.
On the other hand, the pH of the etching solution composition may be 3 or less.
On the other hand, the above-mentioned etching liquid composition may be an etching liquid composition for etching a multilayer film containing copper and titanium.
In another aspect, the present invention provides a method for etching a multilayer film, including a step of contacting a multilayer film including copper and titanium with an etchant composition, wherein the etchant composition includes: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive.
On the other hand, the etching solution composition may not contain hydrogen peroxide or persulfate.
In other aspects, the present invention also provides a method of manufacturing a display device, including: a gate pattern forming step of forming a gate line and a gate electrode connected to each other on a substrate; a data pattern forming step of forming a data line crossing the gate line in an insulating manner, a source electrode connected to the data line, and a drain electrode isolated from the source electrode; forming a pixel electrode connected to the drain electrode; and forming a common electrode insulated from the pixel electrode, wherein at least one of the gate pattern forming step and the data pattern forming step includes a step of forming a metal layer on the substrate and a step of etching the metal layer with an etchant composition.
On the other hand, the etching solution composition may include: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive.
On the other hand, the metal layer may be a multilayer film including a copper film and a titanium film.
On the other hand, the metal layer may be a multilayer film including a copper film and a molybdenum film.
In addition, not all features of the present invention are enumerated in the foregoing solutions for solving the technical problems. The various features of the present invention and the advantages and effects obtained thereby can be understood in more detail with reference to the following detailed description.
ADVANTAGEOUS EFFECTS OF INVENTION
Since the etching solution composition according to various examples of the present invention may not contain hydrogen peroxide or persulfate, it is possible to prevent gas or heat generated by decomposition reaction of the hydrogen peroxide or persulfate, and as a result, it is possible to stably perform etching. In addition, since the pH of the liquid is low, a photoresist lifting phenomenon due to high pH does not occur, and it has an excellent lifespan, a long liquid replacement period, and a reduced amount of waste liquid, and is thus environmentally friendly and economical.
On the other hand, in the case of using the etching solution composition according to various examples of the present invention, there are advantages in that the etching rate of the multilayer film can be freely adjusted, the critical dimension loss can be minimized, the occurrence of etching residues or precipitates can be prevented, the linearity can be maximized, and the surface roughness can be minimized. In addition, in the case of using the etching solution composition of the present invention, the angle of the metal pattern can be freely adjusted, and 40 ° ± 10 ° can be realized.
Drawings
Fig. 1 is a sectional view exemplarily showing an etching result of a multilayer film containing copper and titanium according to an example.
Fig. 2 is a result of observing the etching result of the multilayer film containing copper and titanium of the composition of comparative example 3 with an electron microscope.
Fig. 3 is a result of observing the etching result of the multilayer film containing copper and titanium of the composition of example 2 with an electron microscope.
Fig. 4a and 4b are flowcharts that graphically illustrate a method of manufacturing a display device according to an example.
Fig. 6a, 8a, 9a, and 10a are plan views sequentially showing a method of manufacturing a display device according to an example.
Fig. 5, 6b, 7, 8b, 9b, 10b, and 11 are sectional views sequentially showing a method of manufacturing a display device according to an example.
Fig. 6b, 8b, 9b, 10b are sectional views corresponding to I-I' of fig. 6a, 8a, 9a, 10 a.
Detailed Description
Preferred embodiments of the present invention will be described below. However, the embodiments of the present invention may be modified into various forms, and the scope of the present invention is not limited to the embodiments described below. Furthermore, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
1. Etching liquid composition
The present inventors have made extensive studies to solve the above problems, and as a result, they have found that: in the case of etching a multilayer film comprising copper and titanium using an etching solution composition comprising a combination of a copper ion supply source, an organic acid ion supply source having 1 or more carboxyl groups in the molecule, and a fluorine ion supply source, and additionally comprising a specific additive, not only the problems as described above can be solved, but also various excellent advantages can be obtained.
More specifically, an etching solution composition according to an example includes: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive.
Hereinafter, each component constituting the etching liquid composition according to one example will be described more specifically.
(A) Copper ion supply source
The copper ion supply source (hereinafter, may be simply referred to as component (a)) included in the etching liquid composition according to one example is a component that acts as an oxidizing agent for copper. The copper ion supply source is not particularly limited as long as it can supply copper ions, and for example, inorganic copper salts such as copper sulfate, copper nitrate, copper chloride, copper fluoride, copper phosphide, and copper hydroxide; organic copper salts of acids such as copper acetate, copper citrate, copper lactate, and copper oleate; copper-containing metal salts such as copper silicon compounds, copper bromide and copper carbonate. These copper ion sources may be used alone or in combination of two or more.
On the other hand, although not limited thereto, in one example, among these, copper nitrate, copper sulfate, copper hydroxide, and copper acetate are preferably used as the copper ion supply source, and copper sulfate, copper nitrate, and copper acetate are more preferably used. In this case, the copper can function as an oxidizing agent for copper more effectively.
On the other hand, it is preferable that the etchant composition 1kg contains a copper ion source in an amount of 0.02 to 1.0 mol. When the amount is less than 0.02 mol, the copper etching rate cannot reach a satisfactory level; if the amount exceeds 1.0 mol, the etching rate of copper may be increased, so that it is difficult to control the etching rate and the possibility of precipitation is increased. More preferably in the range of 0.1 to 0.5 mol. When the content of the copper ion source in the etchant composition of one example is within the above range, a further excellent etching rate can be achieved.
(B) Organic acid ion supply source
The organic acid ion supply source (hereinafter, may be simply referred to as component (B)) included in the etching liquid composition according to one example basically forms a complex compound with copper ions to function as an etchant for copper, and also has a function of improving the stability of the etching liquid composition and stabilizing the etching rate. In addition, it is also effective to suppress the generation of residues precipitated when the etching solution composition is diluted with water in the water rinsing step after etching. The organic acid ion source is not particularly limited as long as it is an organic acid compound having 1 or more carboxyl groups in the molecule, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, gluconic acid, citric acid, tartaric acid, malic acid, succinic acid, oxalic acid, maleic acid, and ammonium salts thereof. These organic acid ion sources may be used alone or in combination of two or more.
On the other hand, although not limited thereto, according to the etching liquid composition of one example, among these, an organic acid ion supply source having 2 or more carboxyl groups in the molecule is preferably used. This is because they have good solubility in water, are excellent in stability in an etching solution composition, and can further improve etching performance. More specifically, citric acid, tartaric acid, oxalic acid, maleic acid, ammonium salts thereof, and the like can be preferably used, but the present invention is not limited thereto.
On the other hand, it is preferable that the organic acid ion source is contained in an amount of 0.01 to 3.0 mol per 1kg of the etching solution composition, and if it is less than 0.01 mol, the copper etching rate cannot reach a satisfactory level, and if it exceeds 3.0 mol, the copper etching rate may become high, so that it is difficult to control the etching rate. More preferably, the amount is in the range of 0.1 to 2.0 mol. The mixing ratio of the organic acid ion supply source to the copper ion supply source is preferably 0.01 to 150.0 times, and more preferably 0.1 to 40.0 times on a molar basis. When the content and the mixing ratio of the organic acid ion supply source in the etching liquid composition according to one example are within the above ranges, a more favorable etching rate can be achieved, and the generation of precipitated residues can be more effectively suppressed.
(C) Fluorine ion supply source
The fluorine ion supply source (hereinafter, may be simply referred to as component (C)) included in the etching liquid composition according to one example has a function of improving the etching ability of titanium. The fluorine ion supply source is not particularly limited as long as it can supply fluorine ions, and examples thereof include hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, ammonium fluoroborate, potassium bifluoride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, calcium fluoride, and copper fluoride. These fluorine ion sources may be used alone or in combination of two or more.
On the other hand, although not limited thereto, in the etching liquid composition according to one example, among these, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, and sodium fluoride are preferably used as the fluorine ion supply source, and ammonium fluoride, acidic ammonium fluoride, and potassium fluoride are more preferably used. In this case, the titanium can function as an oxidizing agent.
On the other hand, the fluorine ion source is preferably contained in an amount of 0.01 to 1.0 mol, more preferably 0.1 to 0.5 mol, based on 1kg of the etching solution composition. The mixing ratio of the fluorine ion supply source to the copper ion supply source is preferably 0.01 to 50.0 times, and more preferably 0.01 to 5.0 times on a molar basis. When the content of the fluorine ion source in the etching liquid composition according to one example is within the above range, a more satisfactory etching rate can be achieved, and when the fluorine ion source is less than 0.1 mol, the titanium etching rate cannot reach a satisfactory level, and when it exceeds 1.0 mol, the titanium etching rate may become faster, so that it is difficult to control the etching rate, and the glass as the base material may be seriously damaged.
On the other hand, in the case where the component (C) contains a fluorine ion source having 2 fluorine atoms in 1 molecule, such as acidic ammonium fluoride and acidic potassium fluoride, the content of the component (C) is defined as a 2-fold amount of the content of the fluorine ion source.
Further, the fluorine ion source contained in the etching liquid composition is not a fluorine ion (F) in the liquid－) In the case of dissociation, or as hydrogen difluoride ions (HF)2 －) In some cases, the number of moles of the component (C) is determined on the assumption that the component (C) is completely dissociated.
Further, a copper fluoride salt such as copper fluoride has not only the function as the component (a) but also the function as the component (C). Therefore, in the case where the etching liquid composition according to one example contains a fluoride salt of copper, (a) the content of the component (a) is the content of the other copper ion supply source added to the fluoride salt of copper, and (C) the content of the component (C) is the content of the other fluorine ion supply source added to the fluoride salt of copper.
(D) First additive
The etching solution composition according to one example further includes an etching regulator, a surface oxidizing power improver, or a combination of these as a first additive (hereinafter, may be simply referred to as a (D) component). According to the studies of the present inventors, as described above, when an etching modifier and/or a surface oxidation strength improver as a first additive are further included, the etching rate can be improved and the occurrence of etching residues or precipitates can be remarkably reduced as compared with the case where they are not included. More specifically, in the case where an etching regulator is further included, a better etching rate can be achieved than in the case where it is not included; on the other hand, when the surface oxidation strength improver is further included, the occurrence of etching residue or precipitates can be remarkably reduced.
On the other hand, the above-mentioned Etching regulator is used for the formulation for regulating the Etching Rate (Etching Rate) of the copper layer, and any Etching regulator known in the art may be used without particular limitation as long as the effects as described above can be obtained. For example, although not limited thereto, a supply source of halogen ions other than the above-described fluorine ions, such as hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, bromic acid, potassium bromide, sodium bromide, ammonium bromide, iodic acid, potassium iodide, sodium iodide, ammonium iodide, and the like, can be preferably used. These may be used alone or in combination of plural kinds.
In addition, the surface oxidation force improving agent is used for facilitating the oxidation of the copper surface when etching the copper layer exposed outside the photoresist, thereby enabling the etching to proceed smoothly. As long as the effects described above can be obtained, a surface oxidizing power improver known in the art may be used without particular limitation. For example, although not limited thereto, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, and the like can be preferably used. These may be used alone or in combination of plural kinds. On the other hand, in the case of an inorganic acid including a halogen element such as hydrochloric acid, it also has a function as an etching regulator as described above.
On the other hand, the first additive is preferably included in an amount of 0.01 to 3.0 moles, more preferably 0.1 to 2.0 moles, and still more preferably 0.5 to 1.5 moles, per 1kg of the etching solution composition. The mixing ratio of the first additive to the copper ion source is preferably 0.01 to 150.0 times, more preferably 0.1 to 40.0 times, and still more preferably 1.0 to 15.0 times on a molar basis. When the content of the first additive is less than 0.01 mol, the etching rate may be slower than a target level, or a residue or a precipitate may be generated due to a decrease in surface oxidation force, and when it exceeds 3.0 mol, the etching rate may be increased, which makes it difficult to control the etching rate, or a resist lift-off phenomenon may occur. When the content of the first additive in the etching solution composition according to an example is within the above range, a better etching rate can be achieved and the occurrence of residues or precipitates can be significantly reduced.
(E) Second additive
The etching solution composition according to one example includes a surfactant as a second additive (hereinafter, may be simply referred to as component (E)) in addition to the first additive. According to the studies of the present inventors, as described above, in the case where the surfactant is further included as the second additive, it is possible to maximize linearity, minimize surface Roughness (roughnesss), and freely adjust the angle (Taper)) of the metal pattern, as compared with the case where the surfactant is not included.
On the other hand, the above surfactant is a surfactant generally known in the art, and is not particularly limited as long as it has the effects as described above, and among them, a nonionic surfactant can be preferably used. For example, an alcohol-based nonionic surfactant such as polyethylene glycol, polypropylene glycol, polyether polyol or polyethylene glycol oleate, or a polymer-based compound such as gelatin or an Ethylene Oxide (EO) -Propylene Oxide (PO) copolymer can be used as the nonionic surfactant, but the nonionic surfactant is not limited thereto. These may also be used alone or in combination of plural kinds.
On the other hand, the second additive is preferably included in the etching solution composition 1kg in a range of 1.0 to 30,000ppm, more preferably in a range of 1.0 to 20,000ppm, and still more preferably in a range of 5.0 to 10,000 ppm. When the content of the second additive is less than 1.0ppm, it may be difficult to adjust the angle of the metal pattern within a desired range, and when the content exceeds 30,000ppm, the etching rate of copper may be reduced, and the desired etching rate of copper may not be obtained. In the case where the content of the second additive in the etchant composition according to one example is within the above range, it is possible to effectively maximize linearity, effectively minimize surface roughness, and thus effectively adjust the angle (taper) of the metal pattern to a desired range.
(F) Third additive
The etching solution composition according to one example may further contain an alkali metal salt as a third additive (hereinafter, may be simply referred to as component (F)) as needed, in addition to the first additive and the second additive. According to the studies of the present inventors, as described above, in the case of further containing an alkali metal salt as a third additive, an improvement effect is exhibited in the surface roughness of the metal pattern as compared with the case of not containing it.
On the other hand, the alkali metal salt is not particularly limited as long as the above-described effects can be obtained, and a halogen-containing alkali metal salt such as potassium fluoride, sodium fluoride, potassium chloride, sodium chloride, potassium bromide, sodium bromide, potassium iodide, or sodium iodide; organic acid alkali metal salts having 1 or more carboxyl groups in a molecule, such as potassium citrate, sodium citrate, potassium acetate, sodium acetate, potassium oxalate, and potassium lactate; strongly basic alkali metal salts such as sodium hydroxide and potassium hydroxide. These may also be used alone or in combination of plural kinds.
On the other hand, the third additive is preferably included in an amount of 0.01 to 2.0 mol, more preferably 0.05 to 1.0 mol, and still more preferably 0.1 to 0.5 mol, based on 1kg of the etching solution composition. The mixing ratio of the third additive to the copper ion source is preferably 0.01 to 100.0 times, more preferably 0.05 to 20.0 times, and still more preferably 0.1 to 5.0 times on a molar basis. When the content of the third additive is less than 0.01 mol, the surface roughness of the metal pattern is poor, and when it exceeds 2.0 mol, the copper etching rate may be slow or precipitation may occur. In the case where the content of the third additive in the etching liquid composition according to one example is within the above range, an improved effect is exhibited in the surface roughness of the metal pattern.
On the other hand, the fluorine-containing alkali metal salt such as potassium fluoride or sodium fluoride also has a function as a supply source of fluorine ions as described above, and the alkali metal salt of a halogen other than fluorine such as potassium chloride, sodium chloride, potassium bromide, sodium bromide, potassium iodide, or sodium iodide also has a function as a supply source of a halogen ion other than fluorine ions as described above. Therefore, when the etching liquid composition according to one example contains the fluorine-containing alkali metal salt, the content of the component (C) is the sum of the fluorine-containing alkali metal salt and the other fluorine ion supply source, and the content of the component (F) is the sum of the fluorine-containing alkali metal salt and the other third additive. Similarly, when the etching liquid composition according to one example contains an alkali metal salt of a halogen other than fluorine, (D) is a content of the sum of the other first additive and the alkali metal salt of a halogen other than fluorine, and (F) is a content of the sum of the other third additive and the alkali metal salt of a halogen other than fluorine.
(G) Other additional substances
The etching solution composition according to one example may contain, in addition to the above components, water and various other additives generally used in etching solution compositions for etching as needed within a range not to inhibit the effects of the above etching solution composition. For example, the water is preferably water from which metal ions, organic impurities, particles, and the like have been removed by distillation, ion exchange treatment, filtration treatment, various adsorption treatments, and the like, more preferably pure water, and even more preferably ultrapure water. In this case, the pH adjuster is not particularly limited as long as the effect of the etching solution composition is not inhibited.
On the other hand, the etching liquid composition according to one example is capable of etching a multilayer film containing copper and titanium without containing hydrogen peroxide or persulfate, and therefore may not contain them.
On the other hand, in the etching solution composition according to one example, in order to adjust the angle (Taper)) of the desired metal pattern, an azole-based compound (azole-based compound) generally used in the art may be further included or may not be included.
(H)pH
The pH of the etching liquid composition according to the above example is preferably 3 or less. If the pH exceeds 3, the etching rate may be decreased, and the resist may be lifted off. However, when the pH is too low, the etching rate is too high, and thus, it may be difficult to control the etching time.
2. Etching method of multilayer film
An etching method according to an example is a method of etching a multilayer film containing copper and titanium, which includes a step of contacting the above multilayer film with the etching liquid composition of the present invention as described above.
An etching method according to an example uses a multilayer film containing copper and titanium as an object to be etched. The multilayer film to be an object to be etched may have a multilayer structure including: a copper layer or a layer of a compound having copper as a main component; and a titanium layer or a layer of a compound containing titanium as a main component. The multilayer film includes a 2-layer film in which a layer of a copper layer or a compound containing copper as a main component and a layer of a titanium layer or a compound containing titanium as a main component are laminated, and a 3-layer film in which a layer of a titanium layer or a compound containing titanium as a main component, a layer of a copper layer or a compound containing copper as a main component and a layer of a titanium layer or a compound containing titanium as a main component are laminated.
Examples of copper or a compound containing copper as a main component include copper (metal), copper alloy, copper oxide, and copper nitride. Examples of titanium or a compound containing titanium as a main component include titanium (metal), titanium alloy, and an oxide or nitride thereof.
The object to be etched can be obtained by, for example, forming a multilayer film as described above on a substrate such as glass, applying a resist thereon, exposing and transferring a desired pattern mask, and developing it to form a desired resist pattern. As a substrate on which the multilayer film is formed, for example, a substrate having a layer structure in which a gate wiring is formed on a glass plate and an insulating film made of silicon nitride or the like is provided on the gate wiring, may be used in addition to the above-described glass substrate. In the present invention, a multilayer film wiring provided with a multilayer film (including a layer containing titanium and a layer containing copper) can be obtained by forming a desired multilayer film wiring by bringing an object to be etched into contact with the etching solution composition to etch the multilayer film. Such multilayer film wiring including copper and titanium is preferably used for wiring of a display device such as a flat panel display.
The method of bringing the object to be etched into contact with the etchant composition is not particularly limited, and for example, a wet etching method (wet) may be employed, such as a method of bringing the object into contact with the etchant composition by dropping (single wafer processing) or spraying the etchant composition, or a method of immersing the object in the etchant composition. In the present invention, etching may be performed by any method. In particular, a method of spraying and contacting the etching solution composition to the object to be etched is preferably employed. In addition, as a method of contacting the object by spraying the etching liquid composition, there may be mentioned a method of spraying the etching liquid composition downward from above the object to be etched, a method of spraying the etching liquid composition upward from below the object to be etched, and the like. In this case, the nozzle may be fixed, or an operation such as moving or sliding (sliding) the neck portion may be applied to the nozzle. Further, the nozzle may be disposed so as to face vertically downward or be inclined. The object to be etched may be fixed, or a motion such as swinging or rotating may be applied to the object to be etched, or the object to be etched may be disposed horizontally or inclined.
The temperature of the etchant composition is preferably 10 to 70 ℃, and more preferably 20 to 50 ℃. When the temperature of the etching liquid composition is 10 ℃ or higher, the etching rate becomes good, and therefore, excellent productivity can be obtained. On the other hand, when the temperature of the etching liquid composition is 70 ℃ or lower, the composition change of the liquid can be suppressed, and the etching conditions can be maintained constant. The etching rate also increases as the temperature of the etchant composition is increased, and the optimum treatment temperature may be appropriately determined in consideration of, for example, suppressing the change in the composition of the etchant composition to a small range.
3. Method for manufacturing display device
Fig. 4a and 4b are flowcharts that graphically illustrate a method of manufacturing a display device according to an example.
Referring to fig. 4a, a method of manufacturing a display device according to an example includes: a gate pattern forming step (s100) of forming a gate line and a gate electrode connected to each other on a substrate; a step (s200) of forming a semiconductor pattern on the gate electrode; a data pattern forming step (s300) of forming a data line crossing the gate line in an insulated manner, a source electrode connected to the data line, and a drain electrode isolated from the source electrode; a step (s100) of forming a pixel electrode connected to the drain electrode; and a step (s500) of forming a common electrode insulated from the pixel electrode.
Referring to fig. 4b, at least one of the gate pattern forming step (s100) and the data pattern forming step (s300) includes: a step (s10) of forming a metal layer on the substrate; and a step (s20) of etching the metal layer with an etching solution.
The step (s10) of forming a metal layer on the substrate may include: forming a first metal layer on the substrate; and forming a second metal layer on the first metal layer. The first metal layer may be formed by evaporating a metal including copper, and the second metal layer may be formed by evaporating a metal including titanium or molybdenum.
The etching solution may include: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive.
Fig. 6a, 8a, 9a, and 10a are plan views sequentially showing a method of manufacturing a display device according to an example.
Fig. 5, 6b, 7, 8b, 9b, 10b, and 11 are sectional views sequentially showing a method of manufacturing a display device according to an example.
Fig. 6b, 8b, 9b, 10b are sectional views corresponding to I-I' of fig. 6a, 8a, 9a, 10 a.
The display substrate includes: the liquid crystal display panel comprises an insulating substrate with a plurality of pixel regions, a plurality of grid lines, a plurality of data lines, a plurality of common electrode lines and a plurality of pixels. Since the respective pixels have the same structure, one of the pixels, and two Gate Lines (GL) and two Data Lines (DL) adjacent to the pixel are illustrated for convenience of description.
Referring to fig. 11, the display substrate includes a Thin Film Transistor (TFT) including a gate electrode (1100), a gate insulating film (2000), a semiconductor pattern (2100), a source electrode (2300), and a drain electrode (2500). The thin film transistor is formed by patterning through a photolithography (photolithography) process.
Referring to fig. 5, a first metal layer (ML1) and a second metal layer (ML2) are sequentially stacked on the substrate (1000). The first metal layer may be formed by evaporating a metal including copper, and the second metal layer may be formed by evaporating a metal including titanium or molybdenum.
Referring to fig. 4a, 6a and 6b, the first metal layer (ML1) and the second metal layer (ML2) are etched using an etching solution, thereby forming a Gate Line (GL) and a gate pattern (s100) of a gate electrode (1100) on a substrate (1000). The etching solution may include: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive. The Gate Line (GL) and the gate electrode (1100) may be respectively formed of a first gate metal layer (1100p) and a second gate metal layer (1100 r).
Referring to fig. 7, a gate insulating film (2000) is formed on the substrate (1000) on which the gate electrode (1100) is formed. The gate insulating film (2000) is disposed on the gate electrode (1100) and covers the gate electrode (1100).
Referring to fig. 4a, 8a and 8b, a semiconductor pattern (2100) is formed on the gate insulating film (2000) (s 200). The semiconductor pattern (2100) faces the gate electrode (1100) with the gate insulating film (2000) therebetween.
Referring to fig. 4a, 9a and 9b, a data pattern (s300) is formed on the semiconductor pattern (2100). The data pattern includes a Data Line (DL) crossing the Gate Line (GL) in an insulating manner, and a source electrode (2300) and a drain electrode (2500) connected to the Data Line (DL). The Data Line (DL) may be formed by etching a first data metal layer (not shown) formed by depositing a metal including copper and a second data metal layer (not shown) formed by depositing a metal including titanium or molybdenum with the etchant. The source (2300) may be formed by etching a first source metal layer (2300p) formed by depositing a metal including copper and a second source metal layer (2300r) formed by depositing a metal including titanium or molybdenum with the etchant. The drain electrode (2500) can be formed by etching a first drain electrode metal layer (2500p) formed by depositing a metal including copper and a second drain electrode metal layer (2500r) formed by depositing a metal including titanium or molybdenum with the etching solution. The etching solution may include: (A) a copper ion supply source; (B) an organic acid ion supply source having 1 or more carboxyl groups in a molecule; (C) a fluorine ion supply source; (D) an etching regulator, a surface oxidizing power enhancer, or a combination of these as a first additive; and (E) a surfactant as a second additive. The source (2300) and the drain (2500) are isolated from each other and connected to the semiconductor pattern (2100).
Referring to fig. 10b, an insulating layer (3000) is formed on the source (2300) and the drain (2500). A contact hole (CT) for exposing a part of the upper surface of the drain electrode (2500) is formed in the insulating layer (3000). Further, referring to fig. 3a, 9a, and 9b, a pixel electrode (3100) is formed by patterning a transparent electrode on the insulating layer (3000). The pixel electrode (3100) is disposed on the insulating layer (3000) and electrically connected to the contact hole (CT).
Referring to fig. 4a and 11, a common electrode (4100) insulated from the pixel electrode (3100) is formed (s 500). The common electrode (4100) may be formed on the substrate (1000) on which the color filter substrate (4000) or the thin film transistor is formed. Further, a liquid crystal Layer (LC) may be formed between the substrate (1000) on which the thin film transistor is formed and the color filter substrate (4000).
Examples
The present invention will be described in more detail below with reference to various examples.
Production example 1: manufacture of titanium/copper/titanium/glass substrate
A layer made of titanium (metal) was formed on a glass substrate (size: 150 mm. times.150 mm) by sputtering titanium
Next, a layer made of copper (metal) was formed by sputtering copper
Then, a layer made of titanium (metal) is formed by sputtering titanium
Thus, a 3-layer film structure of titanium/copper/titanium was produced. This was coated with a resist, and a line-shaped pattern mask (line width: 20 μm) was exposed and transferred, followed by development to form a resist pattern, thereby producing a titanium/copper/titanium/glass substrate.
Production example 2: fabrication of copper/titanium/glass substrates
A layer made of titanium (metal) was formed on a glass substrate (size: 150 mm. times.150 mm) by sputtering titanium
Next, a layer made of copper (metal) was formed by sputtering copper
Thus, a 2-layer structure of copper/titanium was produced. A resist was applied thereto, a line-shaped pattern mask (line width: 20 μm) was exposed and transferred, and then a resist pattern was formed by development, thereby producing a copper/titanium/glass substrate.
Comparative example 1: production of etching liquid composition
Into a polypropylene container having a capacity of 100ml, 91.5g of Pure water, 4.0g of copper nitrate (having a molecular weight of 182.56) as a copper ion supply source (a), 4.0g of special grade citric acid (having a molecular weight of 192.13) as an organic acid ion supply source (B), and 0.5g of ammonium fluoride (having a molecular weight of 37.5) as a fluorine ion supply source (C), were put, stirred, and dissolved to prepare an etching solution composition.
The contents of the respective components in the etching liquid composition obtained by the above method were 0.27 mol of the component (a), 0.31 mol of the component (B), and 1.17 times the mixing ratio (mol ratio) of the component (B) to the component (a) per 1kg of the liquid composition. Further, the content of the component (C) was 0.14 mol calculated as 2-fold equivalent of ammonium fluoride in 1kg of the liquid composition. (C) The blending ratio (molar ratio) of the component (a) to the component (a) was 0.5 times. The pH of the resulting etching solution composition was 2.5.
Comparative examples 2 to 3, reference examples 1 to 2, and examples 1 to 5: production of etching liquid composition
An etching solution composition was prepared in the same manner as in comparative example 1 except that the contents of the respective components were as shown in tables 1 and 2.
TABLE 1
TABLE 2
Test example 1: characteristic evaluation 1
The titanium/copper/titanium/glass substrate having a resist pattern formed thereon obtained in production example 1 was etched with the etching solution composition of the example to obtain an evaluation substrate. The obtained evaluation substrates were measured for storage time (storage over time), accumulation time (accumulation over time), liquid reactivity, lifting of photoresist (PR lifting), metal wiring disconnection (pit), presence or absence of precipitates, and a glass reduction amount, and the results are shown in table 3 below. On the other hand, the liquid reactivity is determined based on whether bubbles are generated or not or whether the color of the appearance is changed when the etching solution is left at room temperature; the photoresist lifting is judged according to whether the photoresist is lifted when etching is carried out under the condition of 50% over etching of EPD. Whether or not there is a precipitate is determined based on whether or not the precipitate is generated with the lapse of time (48 times or more) after the etching liquid is dropped onto the evaluation substrate; the amount of reduction in glass was determined by measuring the amount of reduction in the glass substrate due to etching of the titanium layer. Other evaluations were performed by the evaluation methods generally used in the art.
TABLE 3
As can be seen from table 3, the etching solution composition according to one example can minimize the amount of waste solution because of its long life; and because the etching solution has no self-reaction factor, the liquid reactivity is stable; in addition, since the pH is low, a photoresist lifting (PR lifting) phenomenon does not occur; further, there were almost no precipitates, and the evaluation of metal wiring disconnection and reduction in glass amount was also excellent.
Test example 2: characteristic evaluation-2
The titanium/copper/titanium/glass substrate having a resist pattern formed thereon obtained in production example 1 was etched using the etchant compositions of examples, comparative examples, and reference examples to obtain an evaluation substrate. The results of measuring the surface residue, the time of removing the entire multilayer film (EPD), the Critical Dimension loss (CD loss), and the titanium residue (Tailing) of the obtained evaluation substrate are shown in table 4. The measurement method is as follows, and specific meanings of terms are shown in FIG. 1. On the other hand, with respect to the surface residue, the presence/absence of metal residue on the surface of the glass substrate (or the insulating film) was checked; the time at which the copper layer and the titanium layer were removed was measured with respect to the time at which the entire multilayer film was removed. Further, with respect to critical dimension loss, the distance between the end of the photoresist and the end of the copper layer was determined; the distance from the end of the copper layer to the exposed titanium layer was measured for the residue.
TABLE 4
As can be seen from table 4, when the etchant composition according to one example was used, the critical dimension loss (CD loss) and the titanium residue (Tailing) could be minimized. In addition, when the etching regulator is further included as the first additive, the multilayer film total removal time (EPD) can be reduced to 2 minutes or less, and when the surface oxidizing power improver is further included as the first additive, the occurrence of surface residue can be prevented. On the other hand, in the case where the second additive is included in an amount exceeding 30,000ppm, the multilayer film total removal time (EPD) may exceed 2 minutes.
Test example 3: characteristic evaluation-3
The titanium/copper/titanium/glass substrate having a resist pattern formed thereon obtained in production example 1 was etched using the etchant compositions of examples, comparative examples, and reference examples to obtain an evaluation substrate. The angle (Taper), linearity and Roughness (Roughness), and Glass substrate damage (Glass attack) of the metal pattern were measured on the obtained evaluation substrate, and the results are shown in table 5 below. The measurement method is as follows, and specific meanings of terms are shown in FIG. 1. On the other hand, as for the angle of the metal pattern, the angle when the metal pattern is viewed from the cross section is measured; regarding linearity and roughness, it was confirmed whether the insulating film can be normally covered in step coverage (step coverage) of the laminated insulating film after the etching treatment; regarding the damage of the glass substrate, it was confirmed by an electron microscope whether or not the surface of the glass substrate was damaged after the etching treatment.
TABLE 5
As can be seen from table 5, when the etching solution composition according to one example includes the first additive and the surfactant as the second additive, not only linearity and roughness are good, but also damage to the glass substrate can be minimized, and the angle (taper) of the metal pattern can be adjusted to 30 ° to 50 °. In addition, in the case where an alkali metal salt is further included as a third additive, an improvement effect on the roughness of the metal pattern can also be brought about. However, when the azole-based compound is used as the second additive or the content of the contained second additive is less than 1ppm or exceeds 30,000ppm, it may be difficult to adjust the angle (taper) of the metal pattern to 30 ° to 50 °.
Test example 4: characteristic evaluation-4
Resist pattern-formed titanium/copper/titanium etching solution obtained in production example 1 was treated with the etching solution composition of comparative example 3Glass substrate
And the copper/titanium/glass substrate having resist pattern formed thereon obtained in production example 2
After etching was performed under 30% over-etching conditions of EPD, rinsing treatment was performed, and then drying was performed with a blower, and the results of observation were observed with an electron microscope ((a) S-4800, 10.0kV, 10.7mm, x30.0k, SE (M)/(b) SU9000, 10.0kV, x20.0k, SE/(c) S-4800, 10.0kV, 9.8mm, x50.0k, SE (M)/(d) SU9000, 10.0kV, x20.0k, and SE) and are shown in FIG. 2. In this case, (a) and (b) in fig. 2 show the case of etching the glass substrate obtained in production example 1, and (c) and (d) in fig. 2 show the case of etching the glass substrate obtained in production example 2.
In the case of using the etching solution composition of comparative example 3 not including the second additive, as shown in fig. 2(a) and (c), it was found that a taper of 40 ° ± 10 ° could not be achieved.
Test example 5: characteristic evaluation-5
The etching solution composition of example 2 was used to treat the resist pattern-formed titanium/copper/titanium/glass substrate obtained in production example 1
And the copper/titanium/glass substrate having resist pattern formed thereon obtained in production example 2
After etching was performed under 30% over-etching conditions of EPD, rinsing treatment was performed, and then drying was performed by a blower, and observation was performed by an electron microscope ((a) S-4800, 10.0kV, 10.7mm, x30.0k, SE (M)/(b) S-4800, 10.0kV, 12.3mm, x20.0k, SE (M)/(c) S-4800, 10.0kV, 8.5mm, x30.k, SE (M)/(d) S-4800, 10.0kV, 10.6mm, x50.0k, SE (M)/(e) SU9000, 10.0kV, x20.0k, and SE), and the observation results are shown in FIG. 3. In this case, (a), (b) and (c) in FIG. 3 are for the glass obtained in production example 1In the case of etching the substrate, (d) and (e) in fig. 3 are cases of etching the glass substrate obtained in production example 2.
When the etching solution composition according to one example was used, it was found that a taper of 40 ° ± 10 ° could be achieved as shown in fig. 3(a) and (d), and that a pattern linearity could be maximized and a surface roughness could be minimized as shown in fig. 3(b), (c), and (e).
While various embodiments of the present invention have been described in detail, it is apparent to those skilled in the art that the present invention is not limited to these embodiments, and various changes and modifications can be made without departing from the technical spirit of the present invention described in the claims.
Claims (17)
1. An etching solution composition characterized by comprising, in a solvent,
comprises the following steps:
(A) 0.02-1.0 mol/kg of copper ion supply source;
(B) 0.01 to 3.0 mol/kg of an organic acid ion source having 1 or more carboxyl groups in a molecule;
(C) 0.01 to 1.0 mol/kg of a fluorine ion source;
(D) 0.01 to 3.0 mol/kg of an etching regulator, a surface oxidizing power improver, or a combination thereof as a first additive; and
(E) 1.0 to 30,000ppm of a surfactant as a second additive,
wherein the copper ion supply source (A) is at least one selected from the group consisting of copper, copper sulfate, copper nitrate, copper chloride, copper fluoride, copper phosphide, copper hydroxide, copper acetate, copper citrate, copper lactate, copper oleate, copper silicide, copper bromide and copper carbonate,
wherein the organic acid ion source having 1 or more carboxyl groups in the molecule (B) is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, gluconic acid, citric acid, tartaric acid, malic acid, succinic acid, oxalic acid, maleic acid, and ammonium salts thereof,
wherein the fluoride ion supply source (C) is at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, ammonium fluoroborate, potassium bifluoride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, calcium fluoride and copper fluoride,
wherein the mixing ratio of the organic acid ion supply source (B) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis,
wherein the mixing ratio of the fluorine ion supply source (C) to the copper ion supply source (A) is 0.01 to 50.0 times on a molar basis,
wherein the mixing ratio of the first additive (D) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis, and
wherein the pH value of the etching solution composition is below 3.
2. The etching solution composition according to claim 1,
the etching regulator (D) as the first additive is a source for supplying halogen ions other than fluorine ions.
3. The etching solution composition according to claim 2,
the source of the halogen ion other than the fluorine ion is at least one selected from the group consisting of hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, bromic acid, potassium bromide, sodium bromide, ammonium bromide, iodic acid, potassium iodide, sodium iodide, and ammonium iodide.
4. The etching solution composition according to claim 1,
the surface oxidizing power improver (D) as the first additive is an inorganic acid.
5. The etching solution composition according to claim 4,
the inorganic acid is at least one selected from sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid.
6. The etching solution composition according to claim 1,
the surfactant (E) as the second additive is a nonionic surfactant.
7. The etching solution composition according to claim 6,
the nonionic surfactant is at least one selected from polyethylene glycol, polypropylene glycol, polyether polyol, polyethylene glycol oleate, gelatin and ethylene oxide-propylene oxide copolymer.
8. The etching solution composition according to claim 1,
the etching solution composition further includes (F) an alkali metal salt as a third additive.
9. The etching solution composition according to claim 8,
the alkali metal salt of the third additive (F) is at least one selected from the group consisting of a halogen-containing alkali metal salt, an organic acid alkali metal salt having 1 or more carboxyl groups in the molecule, and a strongly basic alkali metal salt.
10. The etching solution composition according to claim 8,
the content of the third additive (F) in the etching solution composition is 0.01-2.0 mol/kg.
11. The etching solution composition according to claim 8,
the mixing ratio of the third additive (F) to the copper ion supply source (A) is 0.01 to 100.0 times on a molar basis.
12. The etching solution composition according to claim 1,
the etching solution composition is used for etching a multilayer film containing copper and titanium.
13. A method for etching a multilayer film, characterized in that,
comprising a step of bringing a multilayer film comprising copper and titanium into contact with an etchant composition,
the etching solution composition comprises: (A) 0.02-1.0 mol/kg of copper ion supply source; (B) 0.01 to 3.0 mol/kg of an organic acid ion source having 1 or more carboxyl groups in a molecule; (C) 0.01 to 1.0 mol/kg of a fluorine ion source; (D) 0.01 to 3.0 mol/kg of an etching regulator, a surface oxidizing power improver, or a combination thereof as a first additive; and (E) 1.0 to 30,000ppm of a surfactant as a second additive,
wherein the copper ion supply source (A) is at least one selected from the group consisting of copper, copper sulfate, copper nitrate, copper chloride, copper fluoride, copper phosphide, copper hydroxide, copper acetate, copper citrate, copper lactate, copper oleate, copper silicide, copper bromide and copper carbonate,
wherein the organic acid ion source having 1 or more carboxyl groups in the molecule (B) is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, gluconic acid, citric acid, tartaric acid, malic acid, succinic acid, oxalic acid, maleic acid, and ammonium salts thereof,
wherein the fluoride ion supply source (C) is at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, ammonium fluoroborate, potassium bifluoride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, calcium fluoride and copper fluoride,
wherein the mixing ratio of the organic acid ion supply source (B) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis,
wherein the mixing ratio of the fluorine ion supply source (C) to the copper ion supply source (A) is 0.01 to 50.0 times on a molar basis,
wherein the mixing ratio of the first additive (D) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis, and
wherein the pH value of the etching solution composition is below 3.
14. The method for etching a multilayer film according to claim 13,
the etching solution composition does not contain hydrogen peroxide and persulfate.
15. A method of manufacturing a display device, characterized in that,
the method comprises the following steps:
a gate pattern forming step of forming a gate line and a gate electrode connected to each other on a substrate;
a data pattern forming step of forming a data line crossing the gate line in an insulating manner, a source electrode connected to the data line, and a drain electrode isolated from the source electrode;
a step of forming a pixel electrode connected to the drain electrode; and
a step of forming a common electrode insulated from the pixel electrode,
wherein at least one of the gate pattern forming step and the data pattern forming step includes a step of forming a metal layer on the substrate and a step of etching the metal layer with an etching liquid composition,
wherein the etching solution composition comprises: (A) 0.02-1.0 mol/kg of copper ion supply source; (B) 0.01 to 3.0 mol/kg of an organic acid ion source having 1 or more carboxyl groups in a molecule; (C) 0.01 to 1.0 mol/kg of a fluorine ion source; (D) 0.01 to 3.0 mol/kg of an etching regulator, a surface oxidizing power improver, or a combination thereof as a first additive; and (E) 1.0 to 30,000ppm of a surfactant as a second additive,
wherein the copper ion supply source (A) is at least one selected from the group consisting of copper, copper sulfate, copper nitrate, copper chloride, copper fluoride, copper phosphide, copper hydroxide, copper acetate, copper citrate, copper lactate, copper oleate, copper silicide, copper bromide and copper carbonate,
wherein the organic acid ion source having 1 or more carboxyl groups in the molecule (B) is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, gluconic acid, citric acid, tartaric acid, malic acid, succinic acid, oxalic acid, maleic acid, and ammonium salts thereof,
wherein the fluoride ion supply source (C) is at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, ammonium fluoroborate, potassium bifluoride, potassium fluoroborate, sodium fluoride, sodium hydrogen fluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, calcium fluoride and copper fluoride,
wherein the mixing ratio of the organic acid ion supply source (B) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis,
wherein the mixing ratio of the fluorine ion supply source (C) to the copper ion supply source (A) is 0.01 to 50.0 times on a molar basis,
wherein the mixing ratio of the first additive (D) to the copper ion supply source (A) is 0.01 to 150.0 times on a molar basis, and
wherein the pH value of the etching solution composition is below 3.
16. The method of manufacturing a display device according to claim 15,
the metal layer is a multilayer film including a copper film and a titanium film.
17. The method of manufacturing a display device according to claim 15,
the metal layer is a multilayer film including a copper film and a molybdenum film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2014-0136592 | 2014-10-10 | ||
| KR1020140136592A KR102331036B1 (en) | 2014-10-10 | 2014-10-10 | Etching solution composition and etching method using the same |
| PCT/KR2015/010586 WO2016056835A1 (en) | 2014-10-10 | 2015-10-07 | Etchant composition, method for etching multilayered film, and method for preparing display device |
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| CN106795633B true CN106795633B (en) | 2021-02-05 |
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| US (1) | US10501853B2 (en) |
| JP (1) | JP6420903B2 (en) |
| KR (1) | KR102331036B1 (en) |
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| CN107604360B (en) * | 2017-09-14 | 2019-10-15 | 江阴江化微电子材料股份有限公司 | A kind of selectivity copper corrosion liquid and application |
| WO2020054296A1 (en) * | 2018-09-12 | 2020-03-19 | 富士フイルム株式会社 | Chemical solution and substrate processing method |
| US11873564B2 (en) * | 2018-10-02 | 2024-01-16 | Hutchinson Technology Incorporated | Etch chemistry for metallic materials |
| CN110202998A (en) * | 2019-06-11 | 2019-09-06 | 中山市佳成塑胶制品有限公司 | A kind of accurate artistic carving of toy product of rubber and plastic |
| US11931805B2 (en) | 2019-12-06 | 2024-03-19 | Colorado School Of Mines | Self-terminating etching processes for post-processing of 3D printed metal alloys |
| CN112680732A (en) * | 2020-12-21 | 2021-04-20 | 江西遂川光速电子有限公司 | Fine line etching liquid |
| US12017276B2 (en) * | 2021-03-17 | 2024-06-25 | Colorado School Of Mines | Self-terminating etching interfaces using iodine-based chemistries |
| CN113078107A (en) * | 2021-06-04 | 2021-07-06 | 苏州华星光电技术有限公司 | Preparation method of array substrate, array substrate and display panel |
| CN115948746B (en) * | 2022-12-30 | 2024-04-30 | 浙江奥首材料科技有限公司 | Al/Mo etching solution, and preparation method and application thereof |
| CN117144366A (en) * | 2023-10-30 | 2023-12-01 | 苏州博洋化学股份有限公司 | Copper etching solution and preparation method thereof |
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| US10501853B2 (en) | 2019-12-10 |
| US20170306501A1 (en) | 2017-10-26 |
| KR102331036B1 (en) | 2021-11-26 |
| JP6420903B2 (en) | 2018-11-07 |
| JP2017537222A (en) | 2017-12-14 |
| KR20160043170A (en) | 2016-04-21 |
| WO2016056835A1 (en) | 2016-04-14 |
| CN106795633A (en) | 2017-05-31 |
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